Facile Oxide to Chalcogenide Conversion for Actinides Using the Boron-Chalcogen Mixture Method.

Actinide chalcogenides are of interest for fundamental studies of the behavior of 5f electrons in actinides located in a soft ligand coordination environment. As actinides exhibit an extremely high affinity for oxygen, the synthesis of phase-pure actinide chalcogenide materials free of oxide impurities is a great challenge and, moreover, requires the availability and use of oxygen-free starting materials. Herein, we report a new method, the boron-chalcogen mixture (BCM) method, for the synthesis of phase-pure uranium chalcogenides based on the use of a boron-chalcogen mixture, where boron functions as an "oxygen sponge" to remove oxygen from an oxide precursor and where the elemental chalcogen effects transformation of the oxide precursor into an oxygen-free chalcogenide reagent. The boron oxide can be separated from the reaction mixture that is left to react to form the desired chalcogenide product. Several syntheses are presented that demonstrate the broad functionality of the technique, and thermodynamic calculations that show the underlying driving force are discussed. Specifically, three classes of chalcogenides that include both new (rare earth uranium sulfides and alkali-thorium thiophosphates) and previously reported compounds were prepared to validate the approach: binary uranium and thorium sulfides, oxide to sulfide transformation in solid-state reactions, and in situ generation of actinide chalcogenides in flux crystal growth reactions.